KR101392629B1 - Resist stripper composition and a method of stripping resist using the same - Google Patents

Abstract

The present invention relates to a resist stripping liquid composition containing (A) a basic compound, (B) a polar solvent, (C) an ammonium salt of (poly) phosphoric acid, (D) an azole-based compound and (E) water, . According to the present invention, it is possible to effectively peel off the resist and etch residue remaining on the substrate during the manufacturing process of a flat panel display such as a liquid crystal display, a plasma display and a flexible display, There is provided a resist stripping liquid composition comprising an ammonium polyphosphate salt and an azole-based compound as a corrosion inhibitor so as not to damage aluminum wiring and copper wiring, and a method of stripping a resist using the same.

Basic compounds, polar solvents, (poly) phosphoric acid ammonium salts, azole compounds, resists, peeling

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist stripping liquid composition and a resist stripping method using the resist stripping liquid composition.

The present invention relates to a resist stripping liquid composition and a resist stripping method using the resist stripping liquid composition. More particularly, the present invention relates to a resist stripping liquid composition which can effectively remove resist patterns and etching residues during fabrication of a flat panel display, And a resist stripping method using the same.

Recently, as the demand for high-resolution implementation of flat panel display (LCD) increases, efforts are being made to increase the number of pixels per unit area. This is accompanied by a gradual decrease in the wiring width of the thin film transistor. In order to cope with miniaturization of such wirings, a dry etching process is introduced, and the process conditions become increasingly severe.

As a result, the required performance of the stripping liquid used in the stripping process, which is a resist stripping process after the completion of the metal pattern, is also enhanced. For example, corrosion resistance of a wet chemical used in a cleaning solution, a peeling solution, and the like due to the ability to remove etching residues generated after a dry etching process and the influence of corrosion on the wiring more as the wiring width becomes narrower The inhibition ability is becoming an important criterion for process application.

In addition, due to the enlargement of the flat panel display, it is required to increase the signal speed in the wiring. Therefore, copper having a lower resistivity than aluminum is being practically used as a wiring material. Accordingly, recent developments of the exfoliating liquid are required to have corrosion inhibiting ability against aluminum and corrosion inhibiting ability against copper.

In recent years, in order to secure price competitiveness of flat panel displays, the demand for price reduction of parts used in the manufacture of flat panel displays is as important as the ability to inhibit corrosion. Therefore, in developing a resist stripper composition, there has been a demand for development of a water-based stripper that can reduce the content of a conventional expensive solvent.

As mentioned above, there are proposed solutions for the removal of resist and etch residues which are denatured by severe process conditions and the corrosion inhibition for aluminum and copper metal wiring, examples of which are as follows.

Korean Patent Laid-Open No. 10-2004-0098751 discloses that a stripper composition to which a stripping promoter is applied in addition to a water-soluble organic amine, a polar solvent, and a corrosion inhibitor can remove a modified or cured resist at a high temperature and a low temperature in a short time . However, the stripper composition has insufficient corrosion inhibiting effect of aluminum and copper wiring metals.

Korean Patent Registration No. 10-0297893 discloses a stripping composition capable of inhibiting metal corrosion by neutralizing an amine using a weak acid having a pK value of 2 or more in a nucleophilic amine. However, the stripping composition is not sufficient to remove the peeling force against the photoresist film denatured and cured by the severe process and the etching residue generated by the reaction with the resist and the metallic by-product in the etching process, The corrosion inhibiting effect is insignificant.

Korean Patent Laid-Open Publication No. 1995-0012144 discloses that alkaline photoresist peeling composition containing a reducing agent can inhibit metal corrosion. However, the peeling composition has not solved the problem of the required sediment removal property and insufficient corrosion resistance to aluminum and copper wiring in a device having a narrow wiring width.

Japanese Patent Application Laid-Open No. 9-152721 discloses a release liquid composition containing an alkanolamine, a hydroxyamine, a diethylene glycol monoalkyl ether, a sugar compound such as sorbitol as a corrosion inhibitor, and water. However, the releasing solution composition is insufficient in peeling force against the photoresist film which is denatured and cured by a severe process, and in the etching process, the etching force for etching residues generated by reaction with the resist and the metallic by-product is insufficient, There is a disadvantage that there is almost no suppression effect.

Korean Patent Laid-Open No. 10-2006-0117666 discloses that a stripper composition comprising water-soluble organic amine, glycol ether, azole and methyl gallate in a polar aprotic solvent can simultaneously prevent corrosion of aluminum and copper. However, the water-based stripper composition of the above composition has insufficient corrosion inhibiting effect on aluminum.

Therefore, in order to solve such a problem in this field, development of a new release liquid composition is required.

As a result, the present inventors have found that when the substrate is treated with the release liquid composition of the present invention comprising a basic compound, a polar solvent, an ammonium polyphosphate, an azole compound, and water, The peelability to the photoresist film, and the corrosion resistance to aluminum and copper are excellent, thereby completing the present invention.

Accordingly, an object of the present invention is to provide a method for manufacturing a flat panel display, which is suitable for removal of residues of a resist and removal of residues after dry and wet etching, and which does not corrode wirings containing aluminum and wirings containing copper, A resist stripper composition capable of reducing cost due to use of a high-priced solvent as a stripper component, and a method for stripping a resist using the stripper composition.

In order to achieve the above object,

(A) a basic compound,

(B) a polar solvent,

(C) (poly) ammonium phosphate,

(D) an azole-based compound, and

(E) water. The present invention also provides a resist stripping liquid composition comprising: (E) water.

In addition, the present invention provides a resist stripping method for removing resist residue and etching residue, which are denatured and cured by high temperature or dry etching, using the resist stripper composition.

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for the production of flat panel displays, in photolithography processes, in which cured and / or altered resist residues and etch residues that occur during wet etching or dry etching are removed without corrosion of the metal lines, A resist stripping liquid composition which can be effectively removed without corrosion of wirings and a stripping method using the same.

 The present invention is based on the total weight of the composition,

(A) 5 to 30% by weight of a basic compound,

(B) 20 to 80% by weight of a polar solvent,

(C) 0.1 to 10% by weight of (poly) phosphoric acid ammonium salt,

(D) 0.1 to 10% by weight of an azole-based compound, and

(E) 5 to 60% by weight of water.

The basic compound (A) used in the resist stripping composition of the present invention may be deteriorated under various process conditions such as dry or wet etching, ashing or ion implant processing, or the like It penetrates strongly into the polymer matrix of the cross-linked resist and breaks bonds existing in the molecule or between molecules. The action of such a basic compound is to form an empty space in a structurally weak part in the resist remaining on the substrate, thereby deforming the resist into amorphous polymer gel state to easily remove the resist attached to the substrate.

Examples of the basic compound include inorganic bases and organic bases.

The inorganic base is preferably a hydroxide including ammonium hydroxide, sodium hydroxide and potassium hydroxide.

As the organic base,

Primary amines including methylamine, ethylamine and monoisopropylamine;

Secondary amines including diethylamine, diisopropylamine and dibutylamine;

Tertiary amines including trimethylamine, triethylamine, triisopropylamine and tributylamine;

(2-hydroxyethyl) piperazine, l- (2-aminoethyl) piperazine, l- (2-hydroxypiperazine, l- Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine and 1- (2-methylpiperazin- Cyclic amines including phenylpiperazine; And

(Ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanol, and N-methyldiethanolamine, Amino-2-propanol, 2- (2-aminoethoxy) ethanol, dimethylaminoethanol, diethylaminoethanol, nitrilo triethanol, 2- Amino-1-propanol, 3-amino-1-propanol, 4-amino-1-butanol and dibutanolamine.

Among the above-mentioned basic compounds, it is more preferable to use a basic compound selected from the group consisting of ammonium hydroxide, tetramethylammonium hydroxide, monoethanolamine and 1-amino-2-propanol. The basic compounds of the present invention are preferably used alone or in combination of two or more.

The basic compound is preferably contained in an amount of 5 to 30% by weight based on the total weight of the composition. When the basic compound is contained in an amount of less than 5% by weight based on the total weight of the composition, the resist stripping effect is insufficient. When the basic compound is contained in an amount exceeding 30% by weight, the corrosion rate against aluminum and copper wiring is rapidly increased . The concentration of the basic compound is one concentration when the basic compound is used singly, and is the total concentration when two or more compounds are used in combination.

The polar solvent (B) used in the resist stripper composition of the present invention serves to increase the solubility of the residue after dry etching or wet etching. In addition, due to the high boiling point, the chemical liquid loss due to volatilization can be minimized when the chemical liquid is used.

As the polar solvent of the present invention, it is preferable to use a mixed solvent of a protonic polar solvent and aprotic polar solvent.

Examples of the protonic polar solvent usable in the present invention include glycol ethers and ester derivatives of glycol ethers, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Ether, and propylene glycol monomethyl ether acetate. These may be used singly or in combination of two or more kinds.

Examples of aprotic polar solvents that can be used in the present invention include pyrrolidone compounds, imidazolidinone compounds, and amide compounds. Specific examples thereof include N-methylpyrrolidone (NMP), N-ethylpyrrolidone Imidazolidinone, 1,3-dipropyl-2-imidazolidinone, N-methylacetamide, dimethylacetamide (DMAc), dimethylformamide (DMF), N- N-dimethylformamide, N, N-dimethylbutylamide, tetramethylenesulfone, gamma -butyrolactone, N, N-dimethylpropionamide, Dimethyl sulfoxide (DMSO), sulfolane, etc. These may be used alone or in admixture of two or more.

The polar solvent is preferably contained in an amount of 20 to 80% by weight, more preferably 30 to 70% by weight based on the total weight of the composition. When the polar solvent is contained in an amount of less than 20% by weight based on the total weight of the total composition, the ability to dissolve the gelled polymer due to the action of the basic compound is insufficient and the peeling performance of the resist may be deteriorated. If included, the removal performance of the dry etch residue may be degraded. The concentration of the polar solvent is a concentration of the total of the mixture of the protonic polar solvent and the aprotic polar solvent.

The (poly) ammonium phosphate which is the component (C) used in the resist stripping composition of the present invention means a salt compound of a phosphate ion or a polyphosphoric acid ion and an ammonium ion, and the phosphate component in the salt compound is a metal, It has an excellent effect on corrosion prevention against aluminum alloy. In addition, the ammonium component has an excellent effect on resist removal.

Specific examples of the ammonium polyphosphate of the present invention include ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium triphosphate, ammonium diphosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium dihydrogenphosphate, ammonium hypophosphite, (Poly) ammonium phosphate represented by W _{n +2} P _n O _{3n +1} (W = NH ₄ , where n is an integer of 2 or more), and these may be used singly or in combination of two or more kinds Can be used. Particularly, among these, it is preferable to use ammonium hydrogen phosphate.

The amount of the (poly) polyphosphoric acid salt is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight based on the total weight of the composition. When the ammonium polyphosphate is contained in an amount of less than 0.1% by weight based on the total weight of the composition, the corrosion inhibiting effect of the composition for removing resist and etch residues on the metal is deteriorated. When the ammonium polyphosphate is contained in an amount exceeding 10% The corrosion inhibiting effect is no longer proportionally increased and the phosphate may remain on the substrate surface. The concentration of the (poly) polyphosphoric acid ammonium salt is one concentration when the (poly) polyphosphoric acid salt is used singly, and the concentration when the two or more kinds are used in combination.

The azole compound used as the component (D) used in the resist stripper composition of the present invention is preferably a triazole compound, and the triazole compound may form a strong bond between the triazole molecule and the metal surface, Thereby preventing penetration of the basic compound, which is a cause of metal corrosion, and preventing corrosion of metals, particularly copper and copper alloys.

Specific examples of the triazole compound include 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-4H- -Triazole, benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, tolyltriazole, benzotriazole- Nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di-t-butylphenol. Of these, benzotriazole, 1-hydroxybenzotriazole, Methylbenzotriazole, 5-methylbenzotriazole, tolyltriazole, 1,2,3-triazole, and mixtures of two or more thereof. desirable.

The azole-based compound is preferably contained in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight based on the total weight of the composition. When the azole-based compound is contained in an amount of less than 0.1% by weight based on the total weight of the composition, the corrosion inhibiting effect of the resist and the etching residue removing composition on the metal is deteriorated. When the azole- It is difficult to proceed with the formation of bubbles at the time of bubbling, and the removal ability of the resist is lowered. The concentration of the azole-based compound is the concentration of one compound when the azole-based compound is used alone, and the concentration thereof when the two or more compounds are used in combination.

Water as the component (E) used in the resist stripping composition of the present invention is easy to dissolve the water-soluble solid compound containing the (poly) ammonium phosphate salt added at the time of preparing the resist stripping composition of the present invention. Also, when the composition of the present invention contains a certain amount of water, the manufacturing cost is lowered. The water is preferably pure water, and examples thereof include deionized water and ultrapure water.

The water content is preferably 5 to 60 wt%, more preferably 10 to 50 wt%, based on the total weight of the composition. When the water content is less than 5% by weight based on the total weight of the total composition, the activity of the basic compound is lowered and the ability to remove the severely modified resist by a severe process such as ashing and dry etching is deteriorated. There arises a problem in the dissolution of the (poly) ammonium phosphate salt used as an anticorrosive agent for aluminum wiring. When the amount of the basic compound or the polar solvent is more than 60 wt%, the peeling force for the resist is decreased due to the decrease of the content of the basic compound or the polar solvent, and the corrosiveness to the metal is increased due to excessive water.

The resist stripping liquid composition of the present invention may further contain an urea compound if necessary, and the contained urea compound has the following functions in the composition. When the urea compound is dissolved in water and converted into a heat or alkaline atmosphere, peroxy ion or hydroxy radical is generated to penetrate the denatured photoresist, thereby forming a dopant ion penetrating the dry etching process in the photoresist Oxidation or reduction. The denatured photoresist in which the dopant has escaped can easily be dissolved by a polar solvent in the composition. The urea compound may also be useful in removing particles generated during the process.

Examples of the urea compound include urea, acetic acid urea, phosphoric acid urea, thiourea, peroxide urea, hydroxy urea, N-methyl urea, 1,1-dimethyl urea, 1,3-dimethyl urea, N, Preferred are monomer compounds such as urea, ethyl urea, 1,3-diethyl urea, phenyl urea, 1,3-diphenyl urea, allyl urea, ethylene urea and cyclohexyl urea, , Thio elements, peroxide elements, hydroxy elements and the like are more preferable, and urea and thiourea are even more preferable. These urea compounds may be used alone or in combination of two or more.

The urea compound is preferably contained in an amount of 0.1 to 5% by weight based on the total weight of the composition. When the urea compound is contained in an amount of less than 0.1% by weight based on the total weight of the composition, it is difficult to realize the effect caused by the inclusion of the urea compound. When the content of the urea compound is more than 5% by weight, There is a possibility of remaining on the substrate after the peeling treatment. The concentration of the urea compound is the concentration of one compound when the urea compound is used alone, and the concentration of the compound when two or more kinds of the urea compound are used in combination.

In addition, the resist stripping composition of the present invention may further comprise a surfactant, if necessary, and the surfactant contained therein increases the wettability to the substrate in the composition so as to achieve uniform cleaning, increases the penetration between the interfaces So as to increase the resist peeling force.

As the surfactant to be used in the present invention, for example, an anionic surfactant, a cationic surfactant and a nonionic surfactant can be used. Among them, a nonionic surfactant having excellent wettability and less bubble formation It is preferable to use an activator.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenyl ether type, polyoxyethylene polyoxypropylene alkyl ether type, polyoxyethylene polyoxybutylene alkyl ether type, polyoxyethylene alkylamino ether type , A polyoxyethylene alkylamido ether type, a polyethylene glycol fatty acid ester type, a sorbitan fatty acid ester type, a glycerin fatty acid ester type, an alkyrol amide type and a glycerin ester type surfactant. The surfactants may be used alone or in combination of two or more.

The surfactant is preferably contained in an amount of 0.001 to 1.0% by weight based on the total weight of the composition. When the amount of the surfactant is less than 0.001% by weight based on the total weight of the entire composition, the uniform peeling effect of the substrate is insignificant. When the amount of the surfactant is more than 1.0% by weight, And the foaming property of the exfoliating liquid tends to become severe, so that the handling tends to be difficult. The concentration of the surfactant is one concentration when the surfactant is used alone, and the concentration when the surfactant is used in combination of two or more.

In the present invention, a compound capable of neutralizing a hydroxyl group produced by an amine as an anticorrosive agent, for example, an organic acid compound or a sugar alcohol compound may be further added, if necessary, Two or more species may be used in combination.

The removing solution composition for removing the photoresist residue of the present invention may be prepared by mixing the above-mentioned compounds in an appropriate amount, and the mixing method is not particularly limited and various known methods can be applied.

The present invention also provides a resist stripping method characterized by using the resist stripper composition of the present invention.

The above-mentioned resist peeling method is a method for peeling a resist,

(I) depositing a conductive metal film on a flat panel display substrate,

(II) forming a resist film on the conductive metal film;

(III) selectively exposing the resist film;

(IV) developing the exposed resist film to form a resist pattern;

(V) etching the conductive metal film using the resist pattern as a mask; And

(VI) a step of peeling the resist, which has been modified and cured by the resist pattern and dry and wet etching after the etching process, from the substrate using the resist stripping liquid composition of the present invention.

In addition, the removing method of the present invention may be carried out by performing a dry etching process such as an etchback process or a CMP (Chemical Mechanical Polishing) process without performing a resist pattern forming process using a mask, And a method of peeling with the peeling liquid composition of the invention.

The resist film forming, exposure, development, etching, and ashing processes in the peeling method can be performed by a method commonly known in the art and are not particularly limited. The resist residues including cured or polymer- A good peeling result can be obtained in a method in which the substrate on which the peeling liquid composition is present can come into contact with the peeling liquid composition.

Examples of the types of the resist include positive and negative g-line, i-line and deep ultraviolet (DUV) resists, electron beam resists, X-ray resists, and ion beam resists. , The resist of the present invention and the composition for removing dry etching residues are particularly effectively applied to a photoresist film composed of a novolak-based phenol resin and a photoactive compound based on diazonaphthoquinone, and a photo It is also effective for a resist film.

As a method for removing the resist on the flat panel display substrate, the modified or cured resist, and the dry etching residue by using the resist stripping liquid composition of the present invention, a method of immersing the substrate coated with the resist in the stripping liquid, And a method of spraying onto a substrate. In this case, physical treatment such as irradiation of ultrasonic waves, rotation, or contact with a brush that rocks to the left and right may be used in combination. After the removing solution treatment, the removing solution remaining on the substrate can be removed by the subsequent cleaning treatment. The cleaning step is the same as the method of treating the exfoliation liquid except that water or isopropyl alcohol is used in place of the exfoliation liquid.

The peeling method may be a deposition method, a spraying method, or a deposition and spraying method. In the case of peeling by immersion, spraying or immersion and spraying, the temperature for peeling is usually from 15 to 100 캜, preferably from 30 to 70 캜, and the immersion, spraying or immersion and spraying time is usually from 30 seconds to 40 minutes, Preferably 1 minute to 20 minutes, but is not strictly applied in the present invention, and can be modified in a condition that is easy and suitable for a person skilled in the art. If the temperature of the release liquid composition applied on the substrate to which the resist is applied is less than 15 캜, the time required to remove the modified or cured resist film may become excessively long. If the temperature of the composition exceeds 100 占 폚, the lower film layer of the resist film may be damaged, resulting in difficulty in handling the exfoliation liquid.

The resist stripper composition of the present invention is a water system type which can increase the activity of a compound in a composition to effectively remove resist and etching residues and is more advantageous than an organic remover at a cost. Compared with the organic peeling liquid, since the composition is low in viscosity similar to water and can be sprayed, it is applicable to a sheet-like method. Therefore, the peeling liquid composition for removing photoresist residue of the present invention can be applied to both a batch method for peeling a plurality of wafers at a time or a single wafer processor for peeling a wafer at a time.

The resist stripping composition of the present invention and the stripping method using the resist stripping composition of the present invention can be used not only for general resist removal but also for removal of resist and etching residue which are modified or cured by etching gas and high temperature. The resist stripper composition of the present invention and the stripping method using the same are advantageous in that they are used in the manufacture of flat panel displays and have excellent corrosion resistance against aluminum and aluminum alloy wiring and metal wiring such as copper and copper alloy wiring have.

The resist stripper composition according to the present invention is excellent in the ability to remove cured resists and dry and wet etching residues in the production of flat panel displays and has excellent corrosion inhibiting effect on aluminum and aluminum alloy wiring and copper and copper alloy wiring outstanding. Therefore, the present invention can be applied to a manufacturing process of a flat panel display having a fine pattern in order to realize a high resolution. Further, when the resist stripper composition according to the present invention is used, the cost of the process can be lowered by reducing the use of the expensive solvent due to a large amount of water.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made.

Example  1 to 4 and Comparative Example  One. Resist Peeling liquid  Preparation of composition

The resist stripper compositions of Examples 1 to 4 and Comparative Example 1 were prepared by mixing the components as shown in Table 1 below.

division Basic
compound
[weight%] Quantum property
Polar solvent
[weight%] Magnetostrictive
Polar solvent
[weight%] Ammonium phosphate salt
[weight%] Azole series
compound
[weight%] Deionized water
[weight%] Example 1 MEA 5 BDG 40 NMP 20 APD One BTA 2 32 Example 2 MEA 20 BDG 40 NMP 20 APD One BTA 2 17 Example 3 MIPA 20 BDG 40 NMP 20 APD One BTA 2 17 Example 4 DBA 20 BDG 40 NMP 20 APD One BTA 2 17 Comparative Example 1 MEA 0 BDG 40 NMP 20 APD One BTA 2 37

Note) MEA: Monoethanolamine

MIPA: Monoisopropanolamine

DBA: Dibutanolamine

BDG: diethylene glycol monobutyl ether

NMP: N-methylpyrrolidone

APD: Ammonium hydrogen phosphate

BTA: benzotriazole

Test Example  1. Depending on the kind and content of basic compounds Resist Removability  evaluation

In order to confirm the peeling effect of the resist stripper composition of Examples 1 to 4 and Comparative Example 1, a Mo / Al / Mo layer was formed on a glass substrate by a thin film sputtering method according to a conventional method, After the resist pattern is formed, a substrate on which a metal film is etched by a wet etching method and a dry etching method is prepared. The resist stripper composition compositions of Examples 1 to 4 and Comparative Example 1 were kept at 70 DEG C constantly in a constant temperature bath, and then the object was immersed for 10 minutes to evaluate the peel force. Thereafter, the substrate was cleaned with deionized water for 1 minute to remove the peeling liquid remaining on the substrate, and the substrate was completely dried with nitrogen to remove deionized water remaining on the substrate after cleaning. The denaturation or curing resist and dry etching residue removal performance of the substrate were confirmed using a scanning electron microscope (SEM, Hitachi S-4700), and the results are shown in Table 2 below.

[Evaluation criteria for peelability]

?: Very good,?: Good,?: Fair, X: bad

division Peeling performance Wet etching substrate Dry etching substrate Example 1 ◎ ◎ Example 2 ◎ ◎ Example 3 ◎ ◎ Example 4 ◎ ○ Comparative Example 1 △ ×

As shown in the results shown in Table 2, the resist stripper compositions of Examples 1 to 4, which are the resist stripper compositions of the present invention, not only have excellent ability to peel off the resist after wet etching, but also have excellent performances for resist and etch residue removal through dry etching Respectively. However, in Comparative Example 1 not containing a basic compound, the peelability was poor.

Example  2, 5 to 13 and Comparative Example  2, 3. Resist Peeling liquid  Preparation of composition

The resist stripping solution compositions of Examples 2, 5 to 13 and Comparative Examples 2 to 3 were prepared by mixing the components as shown in Table 3 below.

division Basic
compound
[weight%] Quantum property
Polar solvent
[weight%] Magnetostrictive
Polar solvent
[weight%] (Poly) phosphoric acid
Ammonium salt
[weight%] Azole series
compound
[weight%] Deionized water
[weight%] Example 2 MEA 20 BDG 40 NMP 20 APD One BTA 2 17 Example 5 MEA 20 BDG 10 NMP 20 APD One BTA 2 47 Example 6 MEA 20 BG 40 NMP 20 APD One BTA 2 17 Example 7 MEA 20 BTG 40 NMP 20 APD One BTA 2 17 Example 8 MEA 20 MDG 40 NMP 20 APD One BTA 2 17 Example 9 MEA 20 BDG 40 NMP 5 APD One BTA 2 32 Example 10 MEA 20 BDG 40 DMSO 20 APD One BTA 2 17 Example 11 MEA 20 BDG 40 DMAc 20 APD One BTA 2 17 Example 12 MEA 20 BDG 40 DMI 20 APD One BTA 2 17 Example 13 MEA 20 BDG 40 Sulpolan 20 APD One BTA 2 17 Comparative Example 2 MEA 20 - - NMP 20 APD One BTA 2 57 Comparative Example 3 MEA 20 BDG 40 - - APD One BTA 2 37

Note) MEA: Monoethanolamine

BDG: diethylene glycol monobutyl ether

BG: Ethylene glycol monobutyl ether

BTG: triethylene glycol monobutyl ether

MDG: diethylene glycol monomethyl ether

NMP: N-methylpyrrolidone

DMSO: dimethylsulfoxide

DMAc: dimethylacetamide

DMI: 1,3-dimethyl-2-imidazolidinone

APD: Ammonium hydrogen phosphate

BTA: benzotriazole

Test Example  2. Depending on the kind and content of polar solvent Resist Removability  evaluation

In order to confirm the peeling effect of the resist stripping liquid compositions of Examples 2, 5 to 13 and Comparative Examples 2 and 3, the same substrate as in Test Example 1 was used, The results are shown in Table 4 below.

[Evaluation criteria for peelability]

?: Very good,?: Good,?: Fair, X: bad

division Peeling performance Wet etching substrate Dry etching substrate Example 2 ◎ ◎ Example 5 ◎ ○ Example 6 ◎ ◎ Example 7 ◎ ◎ Example 8 ◎ ◎ Example 9 ◎ ○ Example 10 ◎ ◎ Example 11 ◎ ◎ Example 12 ◎ ◎ Example 13 ◎ ◎ Comparative Example 2 ○ △ Comparative Example 3 △ ×

As shown in Table 4, the resist stripper compositions of Examples 2 and 5 to 13 exhibited satisfactory stripping performance for resist and etching residue removal by dry etching as well as for resist after wet etching . However, in Comparative Examples 2 and 3 containing the respective solvents other than the mixed solvent of the aprotic polar solvent and the protonic polar solvent, the peeling ability was not good.

Example  2, 14 to 18 and Comparative Example  4, 5. Resist Peeling liquid  Preparation of composition

The resist stripper compositions of Examples 2, 14 to 18 and Comparative Examples 4 to 5 were prepared by mixing the components as shown in Table 5 below.

division Basic
compound
[weight%] Quantum property
Polar solvent
[weight%] Aprotic polar solvent
[weight%] (Poly) phosphoric acid
Ammonium salt
[weight%] Azole series
compound
[weight%] Deionized water
[weight%] Example 2 MEA 20 BDG 40 NMP 20 APD One BTA 2 17 Example 14 MEA 20 BDG 40 NMP 20 APD 0.1 BTA 2 17.9 Example 15 MEA 20 BDG 40 NMP 20 APM One BTA 2 17 Example 16 MEA 20 BDG 40 NMP 20 APT One BTA 2 17 Example 17 MEA 20 BDG 40 NMP 20 APD One BTA 0.5 18.5 Example 18 MEA 20 BDG 40 NMP 20 APD One TTA 2 17 Comparative Example 4 MEA 20 BDG 40 NMP 20 - - BTA 2 18 Comparative Example 5 MEA 20 BDG 40 NMP 20 APD One - - 19

Note) MEA: Monoethanolamine

BDG: diethylene glycol monobutyl ether

NMP: N-methylpyrrolidone

APM: ammonium dihydrogen phosphate

APD: Ammonium hydrogen phosphate

APT: triammonium phosphate

BTA: benzotriazole

TTA: tolyltriazole

Test Example  3. Assessment of Corrosion Prevention Performance by Type and Content of Corrosion Inhibitor

In order to evaluate the corrosion inhibiting performance of Examples 2, 14 to 18 and Comparative Examples 4 and 5, corrosion inhibition performance was evaluated using a copper wiring and a substrate on which Mo / Al / Mo wiring was exposed. Evaluation of the method for aluminum was carried out by immersing in a stock solution for peeling liquid composition at 60 DEG C for 30 minutes and evaluating the method for copper at 60 DEG C for 10 minutes by immersing in a stock solution for peeling liquid composition for 10 minutes, followed by washing and drying and scanning electron microscopy (SEM, Hitach S- 4700). The results are shown in Table 6 below.

[Evaluation criteria for peelability]

?: Very good,?: Good,?: Fair, X: bad

division Corrosion prevention capability Mo / Al / Mo Copper Example 2 ◎ ◎ Example 14 ○ ◎ Example 15 ◎ ◎ Example 16 ◎ ◎ Example 17 ◎ ○ Example 18 ◎ ◎ Comparative Example 4 × ◎ Comparative Example 5 ◎ ×

As shown in the above Table 6, the resist stripping composition of the present invention containing both the (poly) phosphoric acid ammonium salt and the azole-based compound in Examples 2, 14 to 18 exhibited excellent corrosion resistance against both aluminum and copper On the other hand, in Comparative Examples 4 and 5 which did not contain any of the (poly) phosphoric acid ammonium salt and the azole-based compound, it could not be applied to a substrate formed with aluminum and copper wiring simultaneously.

Claims (18)

(A) a basic compound, (B) a polar solvent, (C) (poly) ammonium phosphate, (D) an azole-based compound, and (E) Water Wherein the polar solvent is a mixed solvent of a protonic polar solvent and an aprotic polar solvent, and the (poly) polyphosphoric acid ammonium salt is a corrosion inhibitor for aluminum and an aluminum alloy, Wherein the sol-based compound is a corrosion inhibitor for copper and a copper alloy. The composition according to claim 1, wherein, based on the total weight of the composition, (A) 5 to 30% by weight of a basic compound, (B) polar solvent 20 to 80 wt% (C) 0.1 to 10% by weight of (poly) phosphoric acid ammonium salt, (D) 0.1 to 10% by weight of an azole-based compound, and (E) 5 to 60% by weight of water Wherein the resist stripping liquid composition is a resist stripper composition. The resist stripper composition according to claim 1, wherein the basic compound is an inorganic base or an organic base. The resist stripper composition according to claim 3, wherein the inorganic base is at least one compound selected from the group consisting of ammonium hydroxide, sodium hydroxide, and potassium hydroxide. 4. The method of claim 3, Primary amines including methylamine, ethylamine and monoisopropylamine; Secondary amines including diethylamine, diisopropylamine and dibutylamine; Tertiary amines including trimethylamine, triethylamine, triisopropylamine and tributylamine; (2-hydroxyethyl) piperazine, l- (2-aminoethyl) piperazine, l- (2-hydroxypiperazine, l- Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine and 1- (2-methylpiperazin- Cyclic amines including phenylpiperazine; And (Ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanol, and N-methyldiethanolamine, Amino-2-propanol, 2- (2-aminoethoxy) ethanol, diethylaminoethanol, nitrilotriethanol, 2- Amino-1-propanol, 3-amino-1-propanol, 4-amino-1-butanol and dibutanolamine Wherein the resist stripping liquid composition is one or two or more compounds selected from the group consisting of: delete The method of claim 1, wherein the protonic polar solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, One kind selected from the group consisting of polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and propylene glycol monomethyl ether acetate It is a resist stripper composition, characterized in that two or more kinds of mixed solvents. 2. The process of claim 1, wherein the aprotic polar solvent is selected from the group consisting of N-methylpyrrolidone (NMP), N-ethylpyrrolidone, 1,3-dimethyl- (DMAC), N-methyl-N-ethylpropionamide, diethylacetamide (DEAc), dipropylacetamide (DPAc) , A mixture of one or more kinds selected from the group consisting of N, N-dimethylpropionamide, N, N-dimethylbutylamide, tetramethylene sulfone,? -Butyrolactone, dimethyl sulfoxide (DMSO) Wherein the resist stripping liquid composition is a solvent. 2. The method of claim 1 wherein the ammonium polyphosphate is selected from the group consisting of ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, ammonium diphosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium dihydrogenphosphate, (Poly) ammonium phosphate represented by W _{n + 2} P _n O _{3n +1} (W = NH ₄ , where n is an integer of 2 or more) and ammonium polyphosphate Wherein the resist stripper composition is a resist stripper composition. The method of claim 1, wherein the azole compound is selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, , 4-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, tolyltriazole, benzotriazol- Wherein the compound is at least one compound selected from the group consisting of nitric acid, nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di-t-butylphenol Resist stripper composition. The resist stripper composition according to claim 1, wherein the water is deionized water or ultrapure water. The resist stripper composition according to claim 1, further comprising 0.1 to 5% by weight of urea compound based on the total weight of the total composition. 13. The method of claim 12, wherein the urea compound is selected from the group consisting of urea, acetic acid urea, phosphoric acid urea, thiourea, peroxide urea, hydroxy urea, N-methyl urea, 1,1- One or two selected from the group consisting of dimethyl urea, tetramethyl urea, ethyl urea, 1,3-diethyl urea, phenyl urea, 1,3-diphenyl urea, allyl urea, ethylene urea and cyclohexyl urea Wherein the resist composition is a resist composition. The resist stripper composition according to claim 1, further comprising 0.001 to 1% by weight of a surfactant based on the total weight of the composition. [16] The resist stripper composition according to claim 14, wherein the surfactant is a nonionic surfactant. [Claim 16] The method of claim 15, wherein the nonionic surfactant is selected from the group consisting of a polyoxyethylene alkyl ether type, a polyoxyethylene alkyl phenyl ether type, a polyoxyethylene polyoxypropylene alkyl ether type, a polyoxyethylene polyoxybutylene alkyl ether type, One kind selected from the group consisting of ethylene alkyl amino ether type, polyoxyethylene alkyl amido ether type, polyethylene glycol fatty acid ester type, sorbitan fatty acid ester type, glycerin fatty acid ester type, alkyrol amide type and glycerine ester type surfactants Or a mixture of two or more thereof. (I) depositing a conductive metal film on a flat panel display substrate, (II) forming a resist film on the conductive metal film; (III) selectively exposing the resist film; (IV) developing the exposed resist film to form a resist pattern; (V) etching the conductive metal film using the resist pattern as a mask; And (VI) separating the resist pattern and the resist that has been modified and cured by dry and wet etching after the etching process from the substrate using the resist stripping liquid composition according to any one of claims 1 to 5 and claims 7 to 16 And removing the resist. 18. The method according to claim 17, wherein the conductive metal is at least one selected from the group consisting of copper, aluminum, and an alloy thereof.